EP0162015B1 - Verfahren zur Herstellung von Indolinen - Google Patents
Verfahren zur Herstellung von Indolinen Download PDFInfo
- Publication number
- EP0162015B1 EP0162015B1 EP85810220A EP85810220A EP0162015B1 EP 0162015 B1 EP0162015 B1 EP 0162015B1 EP 85810220 A EP85810220 A EP 85810220A EP 85810220 A EP85810220 A EP 85810220A EP 0162015 B1 EP0162015 B1 EP 0162015B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aminophenyl
- ethanol
- process according
- catalyst
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 24
- 230000008569 process Effects 0.000 title claims description 20
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000002476 indolines Chemical class 0.000 title abstract description 13
- ILDXSRFKXABMHH-UHFFFAOYSA-N 2-(2-aminophenyl)ethanol Chemical compound NC1=CC=CC=C1CCO ILDXSRFKXABMHH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000006210 cyclodehydration reaction Methods 0.000 claims abstract description 14
- 239000012159 carrier gas Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- -1 hydrosilicates Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 0 **(**(*1)=*)C1=* Chemical compound **(**(*1)=*)C1=* 0.000 description 2
- SLRIOXRBAPBGEI-UHFFFAOYSA-N 2-(2-nitrophenyl)ethanol Chemical compound OCCC1=CC=CC=C1[N+]([O-])=O SLRIOXRBAPBGEI-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000002989 Euphorbia neriifolia Species 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
Definitions
- the present invention relates to a process for the preparation of indolines of the formula I, wherein R1 is hydrogen or C1-C4-alkyl, R2 and R3 are each independently hydrogen, C1 ⁇ 4-alkyl or phenyl, by catalytic cyclodehydration of a 2- (2'-aminophenyl) ethanol of the formula II, in which R1, R2 and R3 have the above meaning, in the gas phase.
- the indolines of the formula I are intermediates for the preparation of pyrrolo [3,2,1-i, j] quinolines with bactericidal and fungicidal properties which can be used to combat plant diseases.
- pyrrolo [3,2,1-i, j] quinolines are in British Patents 1,394,373 and 1,394,374.
- 4-Lilolidone (1,2,5,6-tetrahydro-4H-pyrrolo- [3,2,1-i, j] -quinolin-2-one) of the formula III is particularly representative of this class of substances mentioned.
- German patent 606 027 it is known to produce indoline in such a way that 2- (2'-aminophenyl) ethanol is heated to 150-500 ° C., in particular 200-400 ° C., in the presence of a condensing agent.
- the oxides of aluminum, titanium, zirconium, chromium, thor or mixtures of these oxides are mentioned as examples of condensing agents.
- other compounds such as sulfates, phosphates, silicates, hydrosilicates, borates, chlorides, mineral acids, and acid anhydrides can either be used instead of the aforementioned oxides or in a mixture with them as condensing agents.
- indolines can be obtained in good yield by the abovementioned processes, these processes are unsuitable for industrial production of indolines because of the rapid deactivation of the catalysts used and because of the effort associated with the regeneration of the catalysts.
- the indolines of the formula I can be prepared in excellent yield by cyclodehydrating a 2- (2'-aminophenyl) ethanol of the formula II in the gas phase if the cyclodehydration of a 2- (2'-aminophenyl) -ethanol of formula II at 200-350 ° C in the presence of a silicate or an aluminosilicate of an alkaline earth metal or a rare earth metal and in the presence of carrier gas.
- the preferred temperature range for carrying out the reaction is 240-260 ° C. Because of the endothermic nature of the cyclodehydration according to the invention, heat must be added to the system to maintain the reaction temperature.
- the cyclodehydration can be carried out under atmospheric or reduced pressure. It is preferred to work under atmospheric pressure.
- the cyclodehydration is carried out in the presence of carrier gas.
- carrier gas The use of hydrogen, nitrogen, carbonic acid or water vapor as the carrier gas is possible.
- the preferred water vapor as the carrier gas can be used in a ratio of 0.2 to 10 moles per mole of 2- (2'-aminophenyl) ethanol.
- the use of 3 to 5 moles of water vapor per mole of 2- (2'-aminophenyl) ethanol is particularly preferred.
- Water can be added via separate water or steam lines or by leading the correspondingly concentrated aqueous solution of 2- (2'-aminophenyl) ethanol into the reactor via an evaporator.
- the alkaline earth metal silicate catalysts which can be used for the cyclodehydration according to the invention can be reacted with an alkali water glass dissolved in water, e.g. Potash water glass with the aqueous solution of an alkaline earth metal salt, e.g. Magnesium nitrate, by filtering, washing and drying the resulting and precipitated alkaline earth metal silicate and by activating it by air passage at temperatures of 300 to 550 ° C.
- an alkali water glass dissolved in water e.g. Potash water glass
- an alkaline earth metal salt e.g. Magnesium nitrate
- the preferred temperature range for the activation of the alkaline earth silicate catalysts is 340-360 ° C.
- the magnesium silicate is preferably used.
- Suitable catalysts for the cyclodehydration according to the invention are the synthetic or natural molecular sieves belonging to the group of silicates or aluminosilicates.
- Such molecular sieves with cations of alkaline earth or rare earth metals can be produced from the synthetic molecular sieves containing alkali metal cations by ion exchange, as described in company documents. (Eg: "Linde Molecular Sieves, Catalyst Bulletin, Union Carbide", 270 Park Ave., New York, NY 10017, USA).
- catalysts which mainly contain cations of rare earth metals, are also preferred as catalysts. Such catalysts are commercially available.
- the catalyst offered under the name Strem 14-8910 is, for example, an alumino-silicate molecular sieve enriched with rare earths with the following composition: SiO2 65.0% Al2O3 22.7% Na2O 1.6% Re2O3 10.7%, where Re means the sum of all cations of rare earth metals.
- moving bed reactors e.g. a fluidized bed reactor or fixed bed reactors are used.
- the activation or reactivation of the catalyst can take place in one of the reactors mentioned, in parallel with the reaction or alternately therewith.
- the method according to the invention is suitable for continuous process control.
- the inventive method is generally applicable for the preparation of the indolines of the formula I, wherein R1 is hydrogen or C1-C4-alkyl, R2 and R3 are each independently hydrogen, C1 Wasserstoff-alkyl or phenyl.
- C1-C4-alkyl includes methyl, ethyl, n-propyl, isopropyl, primary and secondary n-butyl, isobutyl and tert-butyl.
- the 2- (2'-aminophenyl) ethanol is in the presence of Mg silicate and with the addition of 3-5 moles of water vapor per mole of 2- (2'-aminophenyl) ethanol at 240- Cyclodehydrated 260 ° to indoline.
- the substituted 2- (2'-aminophenyl) ethanols used for the cyclodehydration according to the invention can be prepared by reducing the corresponding nitro compounds.
- the 2- (2'-aminophenyl) ethanol is also readily available from the 2- (2'-nitrophenyl) ethanol by reduction with zinc according to Sabetay (Bull. Soc. Chim. Fr. 1931, 49 3).
- the 2- (2'-nitrophenyl) ethanol and its substituted derivatives can be obtained by adding o-nitroalkylbenzenes to an aldehyde according to Japanese Patent 77-108941; CA Vol. 88 (1978) 104875x can be produced according to the following reaction scheme:
- indolines can be prepared by catalytic cyclodehydration of 2- (2'-aminophenyl) ethanols with a selectivity of more than 97% with a conversion of at least 98%, the life of the catalyst advantageously being compared to the processes known hitherto is extended many times. According to the invention, this advantageous effect is achieved by adding carrier gas.
- 3 ml of the catalyst thus prepared are placed in the catalyst bed of a microreactor. 3 ml / hour of a 65% aqueous solution of 2- (2'-aminophenyl) ethanol are metered into the reactor at atmospheric pressure. The temperature of the catalyst is kept at 260 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Catalysts (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT85810220T ATE70052T1 (de) | 1984-05-16 | 1985-05-09 | Verfahren zur herstellung von indolinen. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61072784A | 1984-05-16 | 1984-05-16 | |
| US610727 | 1996-03-04 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0162015A2 EP0162015A2 (de) | 1985-11-21 |
| EP0162015A3 EP0162015A3 (en) | 1988-07-06 |
| EP0162015B1 true EP0162015B1 (de) | 1991-12-04 |
Family
ID=24446177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85810220A Expired - Lifetime EP0162015B1 (de) | 1984-05-16 | 1985-05-09 | Verfahren zur Herstellung von Indolinen |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0162015B1 (xx) |
| JP (1) | JPS60246366A (xx) |
| KR (1) | KR920001464B1 (xx) |
| AT (1) | ATE70052T1 (xx) |
| DE (1) | DE3584791D1 (xx) |
| ZA (1) | ZA853689B (xx) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4886887A (en) * | 1985-11-08 | 1989-12-12 | Ciba-Geigy Corporation | Process for the preparation of indolines |
| JPS63196561A (ja) * | 1987-02-07 | 1988-08-15 | Idemitsu Kosan Co Ltd | インド−ル類の製造方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE606027C (de) * | 1933-11-16 | 1934-11-23 | I G Farbenindustrie Akt Ges | Verfahren zur Herstellung von Indolinen und Indolen |
| JPS52108969A (en) * | 1976-03-09 | 1977-09-12 | Mitsui Petrochem Ind Ltd | Preparation of indolines |
| JPS52142063A (en) * | 1976-05-19 | 1977-11-26 | Mitsui Petrochem Ind Ltd | Preparation of indoles |
| HU177029B (hu) * | 1979-05-29 | 1981-06-28 | Reanal Finomvegyszergyar | Sposob poluchenija indola,1,283,4-tetragidrokhinolina i ikh proizvodnykh |
| JPS5835171A (ja) * | 1981-08-25 | 1983-03-01 | Mitsui Toatsu Chem Inc | インド−ルの改良された製造方法 |
-
1985
- 1985-05-09 EP EP85810220A patent/EP0162015B1/de not_active Expired - Lifetime
- 1985-05-09 AT AT85810220T patent/ATE70052T1/de not_active IP Right Cessation
- 1985-05-09 DE DE8585810220T patent/DE3584791D1/de not_active Expired - Lifetime
- 1985-05-14 JP JP60100659A patent/JPS60246366A/ja active Granted
- 1985-05-15 ZA ZA853689A patent/ZA853689B/xx unknown
- 1985-05-15 KR KR1019850003319A patent/KR920001464B1/ko not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ZA853689B (en) | 1985-12-24 |
| ATE70052T1 (de) | 1991-12-15 |
| JPS60246366A (ja) | 1985-12-06 |
| DE3584791D1 (de) | 1992-01-16 |
| EP0162015A3 (en) | 1988-07-06 |
| KR920001464B1 (ko) | 1992-02-14 |
| KR850008338A (ko) | 1985-12-16 |
| JPH0471909B2 (xx) | 1992-11-16 |
| EP0162015A2 (de) | 1985-11-21 |
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